CN101502785B - Method for preparing nano titanates for removing surface modification of heavy metal ion - Google Patents
Method for preparing nano titanates for removing surface modification of heavy metal ion Download PDFInfo
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- CN101502785B CN101502785B CN2008102437366A CN200810243736A CN101502785B CN 101502785 B CN101502785 B CN 101502785B CN 2008102437366 A CN2008102437366 A CN 2008102437366A CN 200810243736 A CN200810243736 A CN 200810243736A CN 101502785 B CN101502785 B CN 101502785B
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Abstract
The invention discloses a method for preparing surface modified nano titanate for removing heavy metal ions, which comprises the following steps: firstly, preparing chitosan modifying agent solution, placing nano titanate into the modifying agent solution to form suspension solution, heating the suspension solution at a temperature between 40 and 120 DEG C, and condensing and reflowing the suspension solution for more than 3 hours; and separating out sediment, and drying the sediment to obtain the modified nano titanate. The method uses metatitanic acid or titanyl sulfate or nano titanium oxide as a raw material, adopts a hydro-thermal method, synthesizes the nano titanate by controlling the category of the raw materials, the category and concentration of alkali and the reaction temperature, and uses a reflow method to carry out surface modification for the nano titanate, thereby obtaining better effect of removing the heavy metal ions.
Description
Technical field:
The present invention relates to a kind of Hydrothermal Preparation that adopts and efficiently remove the true Nano titanate modification technique of heavy metal ion.
Background technology:
With the high speed development of economic society, multiple industry waste water such as mining, metallurgy, chemical industry, plating discharge in a large number, cause heavy metal ion also more and more serious to the pollution and the harm of environment.Reducing heavy metal ion has become the focus of world today's concern to the pollution of environment.At present, remove that the method for heavy metal ion has chemical precipitation method, membrane filter method, ion-exchange, CAM and co-precipitation/absorption method and biological treatment etc. in the water quality.
The nano barium titanate salt material has layer structure, and interlayer ion has good ion exchangeable, can be by the heavy metal ion in the ion-exchange treatment waste water.Nano titanate has bigger specific surface than block, if again finishing some can adsorb the material of heavy metal, be expected to obtain the effect of better removal heavy metal ion.
Summary of the invention:
The object of the present invention is to provide a kind of Nano titanate preparation method who newly is used to remove the finishing of heavy metal ion,, improved the effect of removing heavy metal ion greatly through the Nano titanate of finishing.
Technical scheme of the present invention is as follows:
Be used to remove the Nano titanate preparation method of the finishing of heavy metal ion, it is characterized in that may further comprise the steps successively:
(1), the aqueous acetic acid with 0.5～2% is solvent, the modifier solution of preparation mass concentration 0.1～1.5% dissolves modifier under 40～60 ℃ of stirrings fully;
(2) get Nano titanate and be put in the above-mentioned solution, stirring and dissolving is made aaerosol solution, and the Nano titanate mass concentration is 0.1～40% in the aaerosol solution.
(3), be heated to 40～120 ℃ of down reactions more than 3 hours, and condensing reflux;
(4), filtration or centrifugation go out sediment, repeatedly washing, until the PH of cleaning solution till the neutrality;
(5), sediment oven dry, promptly get the Nano titanate of modification;
Described modifier is shitosan or chitosan quaternary ammonium salt or CMC.
The described Nano titanate preparation method who is used to remove the finishing of heavy metal ion, it is characterized in that: the preparation method of chitosan quaternary ammonium salt is:
(1), take by weighing shitosan in reactor, add isopropyl alcohol, water-bath is stirred 1～2h down for 20～40 ℃, makes the abundant swelling of shitosan;
(2), configuration quality concentration is the aqueous solution of 30～60% quaternary amine, quaternary amine is selected hydroxypropyl-trimethyl ammonium chloride or epoxypropyl trimethylammonium chloride ammonium for use;
(3), the shitosan bath temperature is elevated to 70～90 ℃, be 3～8: 1 by quaternary amine and shitosan mol ratio, gradation adds the aqueous solution of quaternary amine, and 8～12h refluxes;
(4), reflux to finish after, product after filtration, after the washing, suction filtration, use ethanol extracting 12-24h again, final drying obtains chitosan quaternary ammonium salt.
3, the Nano titanate preparation method who is used to remove the finishing of heavy metal ion according to claim 1, it is characterized in that: the Preparation of Carboxymethylchitosan method is:
(1), take by weighing shitosan in reaction vessel, add isopropyl alcohol, water-bath 20-35 ℃ is stirred 1～2h down, makes the abundant swelling of shitosan;
(2), in reaction vessel, add 5～10mol/L NaOH solution, stir 10～16h down at 40～60 ℃, the mol ratio of NaOH and shitosan is 150～250: 1;
(3), take by weighing monoxone, the mol ratio of monoxone and shitosan is 60～120: 1, under stirring, gradation adds in the chitosan solution, 50～80 ℃ add hot reflux 4～6h;
(4), reflux to finish after, in flask, add acetum again, transfer PH to neutral.
(5), product after filtration, after the washing, suction filtration, use ethanol extracting 12～24h, after 80～100 ℃ of oven dryings obtain CMC again.
4, the Nano titanate preparation method who is used to remove the finishing of heavy metal ion according to claim 1 is characterized in that described Nano titanate is meant titanate nanotube or titanate nanometer sheet, nanometer silk ribbon, sterculia seed shape nanostructured, sea urchin shape nanostructured, micro-nano apparatus derivatorius.
5, the Nano titanate preparation method who is used to remove the finishing of heavy metal ion according to claim 1 is characterized in that described sediment oven dry promptly gets product.
The present invention is raw material with metatitanic acid or titanyl sulfate or nano-titanium oxide, adopt hydro-thermal method, come the synthesis of nano titanate by kind and concentration, the reaction temperature of controlling raw-material kind, alkali, by circumfluence method Nano titanate is carried out surface modification, obtain the effect of better removal heavy metal ion.
Description of drawings
Fig. 1: Nano titanate and chitin modified after the Nano titanate XRD spectra.
The specific embodiment
Example 1:
Chitin modified Nano titanate preparation method:
(1), preparation 0.1～1.5% chitosan solution, get 0.2～3g shitosan and be added in the 500mL beaker, thin up is to 200mL, 30～60 ℃ were stirred 1～2 hour, and then the acetic acid that adds 2～4ml is in beaker, stirred shitosan is dissolved fully.
(2), get Nano titanate 2～30g in chitosan solution, stir.
(3), be heated to 40～120 ℃ of down reactions more than 3 hours, and condensing reflux;
(4), reflux to finish after, filter or centrifugation goes out sediment, repeatedly washing, until the PH of solution till the neutrality.
(5), sediment oven dry, promptly get chitin modified Nano titanate.
Fig. 1 be Nano titanate and chitin modified after the Nano titanate XRD spectra.
Example 2:
The Nano titanate preparation method of chitosan quaternary ammonium salt modification:
(1), the preparation of shitosan quaternary amine.
A) take by weighing 1～2g shitosan in the 250ml flask, add the isopropyl alcohol of 10～30ml, water-bath is stirred 1～2h for 30 ℃, makes the abundant swelling of shitosan.
B) be 3～8: 1 by quaternary amine and shitosan mol ratio, the configuration quality mark is the aqueous solution 100ml of 30～60 quaternary amine.Optional hydroxypropyl-trimethyl ammonium chloride of quaternary amine or epoxypropyl trimethylammonium chloride ammonium etc.
C) bath temperature that will place the shitosan flask is elevated to 70～90 ℃, divides the aqueous solution that adds quaternary amines for 3～5 times, and 8～12h refluxes.
D) reflux to finish after, product is after filtration, after the washing, suction filtration, use ethanol extracting 24h, after 80～100C oven drying obtains chitosan quaternary ammonium salt again.
(2), get Nano titanate 2～30g, put into the conical flask of 500ml, add 300ml water, stir, obtain white suspension solution.
(3), add 0.5～1g chitosan quaternary ammonium salt in white suspension solution, more than 40～120 ℃ of condensing reflux 3h.
(4), reflux to finish after, filter or centrifugation goes out sediment, repeatedly washing, till the neutrality, the sediment oven dry promptly gets the Nano titanate of chitosan quaternary ammonium salt modification until the PH of solution.
Example 3:
The CMC modification the Nano titanate preparation method:
(1), Preparation of Carboxymethylchitosan.
A) take by weighing 4～8g shitosan in the 250ml flask, add the isopropyl alcohol of 40～80ml, water-bath is stirred 1～2h for 30 ℃, makes the abundant swelling of shitosan.
B) add the 10mol/LNaOH of 10～20ml in flask, 40～60 ℃ are stirred 10～16h.
C) claim 6～10g monoxone, under stirring, divide to add in the chitosan solution for 3～5 times, 50～80C, the 4～6h that refluxes.
D) after backflow finishes, in flask, add acetic acid again, transfer PH to neutral.
Product after filtration, after the washing, suction filtration, use ethanol extracting 24h, after 80～100 ℃ of oven dryings obtain CMC again.
(2), get Nano titanate 2～30g, put into the conical flask of 500ml, add 300ml water, stir, obtain white suspension solution.
(3), add 0.5～1g CMC in white suspension solution, 70～90 ℃ of condensing reflux 4～6h.
(4), reflux to finish after, filter or centrifugation goes out sediment, repeatedly washing, till the neutrality, the sediment oven dry promptly gets the Nano titanate of CMC modification until the PH of solution.
Product is described:
The crystalline phase of Nano titanate is Na
2Ti
2O
5, be rhombic system, lattice paprmeter a=1.68nm, b=0.375nm, c=0.306nm.
Before and after the modification, the XRD figure spectrum does not change substantially.
Following table: the 10mg shitosan, the sample of epoxypropyl trimethylammonium chloride ammonium shitosan and CMC modification is to 8ml 100mg/L, Cd
2+, Pb
2+, Cu
2+, Fe
3+, Ni
2+, Cr
6+Clearance
| The metal ion clearance | Chitin modified | The epoxypropyl trimethylammonium chloride ammonium is chitin modified | The CMC modification |
| Cd 2+ | 81.1? | 85.2? | 90.2? |
| Pb 2+ | 92.1? | 93.4? | 93.1? |
| Cu 2+ | 88.3? | 90.5? | 92.5? |
| Fe 3+ | 86.2? | 92.2? | 88.7? |
| Ni 2+ | 80.6? | 91.6? | 94.6? |
| Cr 6+ | 89.1? | 94.1? | 93.1? |
Claims (4)
1. be used to remove the Nano titanate preparation method of the finishing of heavy metal ion, it is characterized in that may further comprise the steps successively:
(1), the aqueous acetic acid with 0.5～2% is solvent, the modifier solution of preparation mass concentration 0.1～1.5% dissolves modifier under 40～60 ℃ of stirrings fully;
(2) get Nano titanate and be put in the above-mentioned solution, stirring and dissolving is made aaerosol solution, and the Nano titanate mass concentration is 0.1～40% in the aaerosol solution;
(3), be heated to 40～120 ℃ of down reactions more than 3 hours, and condensing reflux;
(4), filtration or centrifugation go out sediment, repeatedly washing, until the pH of cleaning solution till the neutrality;
(5), sediment oven dry, promptly get the Nano titanate of modification;
Described modifier is shitosan or chitosan quaternary ammonium salt or CMC.
2. the Nano titanate preparation method who is used to remove the finishing of heavy metal ion according to claim 1, it is characterized in that: the preparation method of chitosan quaternary ammonium salt is:
(1), take by weighing shitosan in reactor, add isopropyl alcohol, water-bath is stirred 1～2h down for 20～40 ℃, makes the abundant swelling of shitosan;
(2), configuration quality concentration is the aqueous solution of 30～60% quaternary ammonium salt, quaternary ammonium salt is selected hydroxypropyl-trimethyl ammonium chloride or epoxypropyl trimethylammonium chloride ammonium for use;
(3), the shitosan bath temperature is elevated to 70～90 ℃, be 3～8: 1 by quaternary ammonium salt and shitosan mol ratio, gradation adds the aqueous solution of quaternary ammonium salt, and 8～12h refluxes;
(4), reflux to finish after, product after filtration, after the washing, suction filtration, use ethanol extracting 12-24h again, final drying obtains chitosan quaternary ammonium salt.
3. the Nano titanate preparation method who is used to remove the finishing of heavy metal ion according to claim 1, it is characterized in that: the Preparation of Carboxymethylchitosan method is:
(1), take by weighing shitosan in reaction vessel, add isopropyl alcohol, water-bath 20-35 ℃ is stirred 1～2h down, makes the abundant swelling of shitosan;
(2), in reaction vessel, add 5～10mol/LNaOH solution, stir 10～16h down at 40～60 ℃, the mol ratio of NaOH and shitosan is 150～250: 1;
(3), take by weighing monoxone, the mol ratio of monoxone and shitosan is 60～120: 1, under stirring, gradation adds in the chitosan solution, 50～80 ℃ add hot reflux 4～6h;
(4), reflux to finish after, in flask, add acetum again, transfer pH to neutral.
(5), product after filtration, after the washing, suction filtration, use ethanol extracting 12～24h, after 80～100 ℃ of oven dryings obtain CMC again.
4. the Nano titanate preparation method who is used to remove the finishing of heavy metal ion according to claim 1 is characterized in that described Nano titanate is meant titanate nanotube or titanate nanometer sheet, nanometer silk ribbon, sterculia seed shape nanostructured, sea urchin shape nanostructured.
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| CN103406089B (en) * | 2013-07-22 | 2014-12-17 | 沈阳理工大学 | Method for preparation of rime-like titanate by taking organic matters in methacrylic acid wastewater as template agent |
| CN105944656A (en) * | 2016-05-16 | 2016-09-21 | 成都信息工程大学 | Titanium-based heavy metal ion adsorbent as well as preparation method and application thereof |
| CN106179196B (en) * | 2016-07-15 | 2018-06-19 | 中信国安化工有限公司 | A kind of petrochemical wastewater processing adsorbent and preparation method thereof |
| CN107469760B (en) * | 2017-09-28 | 2020-06-26 | 江苏大学 | Nano CaTiO3Powder adsorbent and preparation method and application thereof |
| CN108499541B (en) * | 2018-04-08 | 2019-10-18 | 山东建筑大学 | A kind of titanium sulfate-chitosan compounding filter aid and preparation method thereof |
| CN113862252B (en) * | 2021-10-28 | 2022-09-27 | 江苏奕农生物股份有限公司 | Method for immobilizing laccase by titanate nanotube composite material |
| CN114291843B (en) * | 2022-01-07 | 2023-09-29 | 中国科学院东北地理与农业生态研究所 | Multistage sodium titanate microtube and preparation method and application thereof |
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